阅读说明：本技术 一种氯丁橡胶粘合剂及其制备方法 (Chloroprene rubber adhesive and preparation method thereof ) 是由 陆雪龙 苏福男 胡银 于 2019-10-10 设计创作，主要内容包括：本发明涉及橡胶粘合剂,公开了一种氯丁橡胶粘合剂及其制备方法,本发明将氯丁橡胶进行研磨,加入己烷烃类溶剂搅拌至氯丁橡胶充分溶解,另一方面,结合含有亚硝基氟橡胶生胶的组合物B、增粘树脂、交联剂、氧化镁和氧化锌,得到了粘性与黏合持久性均较强的粘合剂。不仅如此,该粘合剂的制备方法简单,环保,粘合过程易于控制,具有较高的推广应用价值。(The invention relates to a rubber adhesive, and discloses a chloroprene rubber adhesive and a preparation method thereof. Moreover, the preparation method of the adhesive is simple, environment-friendly, easy to control the bonding process and high in popularization and application value.)

1. The preparation method of the chloroprene rubber adhesive is characterized by comprising the following steps:

(1) grinding the chloroprene rubber, adding a hexane hydrocarbon solvent, and stirring until the chloroprene rubber is fully dissolved, wherein the mass concentration of the chloroprene rubber is 50-60%, so as to obtain a composition A;

(2) dissolving raw nitroso-fluoro rubber in dimethoxymethane at the mass concentration of 50-60% to prepare a solution, thus obtaining a composition B;

(3) and mixing the composition A, the composition B, tackifying resin, a crosslinking agent, magnesium oxide and zinc oxide to obtain the chloroprene rubber adhesive.

2. The method according to claim 1, wherein the hexane hydrocarbon solvent is a mixture of n-hexane and cyclohexane in a ratio of 1: 2-3.

3. The production method according to claim 1, wherein the amount of composition B is 40 to 50 parts, the amount of tackifier resin is 8 to 10 parts, the amount of crosslinking agent is 10 to 15 parts, the amount of magnesium oxide is 2 to 3 parts, and the amount of zinc oxide is 2 to 3 parts, in parts by mass, relative to 100 parts of composition a.

4. The method according to any one of claims 1 to 3, wherein the step (3) further comprises adding an anti-aging agent and an antioxidant.

5. The production method according to claim 4, wherein the age resistor is used in an amount of 0.5 to 2 parts by weight and the antioxidant is used in an amount of 0.5 to 2.5 parts by weight, based on 100 parts by weight of the composition A.

6. The production method according to any one of claims 1 to 3, wherein the tackifier resin is at least one of a rosin, a polymerized rosin, a rosin glycerin ester, a rosin pentaerythritol ester, a petroleum resin, a terpene resin, and a rosin-modified phenol resin.

7. The production method as claimed in any one of claims 1 to 3, wherein the chloroprene rubber is a chloroprene rubber having an elongation at break of 850-1000%, a rebound resilience of 60-80% and a hardness of 55-70shore a.

8. The production process according to any one of claims 1 to 3, wherein the raw nitroso-fluoro rubber has an intrinsic viscosity of 0.05 to 0.06dLg^-1The physical form of the material is liquid form and has room temperature flowability.

9. The method according to any one of claims 1 to 3, wherein the crosslinking agent is one or a combination of any two or more of an organic polyamine, a low molecular weight polyetheramine, an aziridine, and a polycarbodiimide.

10. A chloroprene rubber adhesive produced by the production method according to any one of claims 1 to 9.

Technical Field

The invention relates to an adhesive, in particular to a chloroprene rubber adhesive and a preparation method thereof.

Background

Rubber products, in particular rubber shoes, require high adhesive requirements for rubber shoes due to the special characteristics of the use environment, otherwise, the adhesive part between the upper and the sole is easy to crack.

The rubber adhesive is widely applied in the preparation process of rubber products, and the chloroprene rubber adhesive is used as one of the rubber adhesives and is commonly used in adhesives for plastics, but the chloroprene rubber adhesive used in the prior art is usually formed by singly combining chloroprene rubber and a solvent, so that the phenomena of infirm bonding, easy loosening and the like are often caused in the process of bonding rubber products, particularly bonding different rubber products, so that the bonding effect is poor, and the product quality is greatly influenced.

Chinese patent application 201410225215.3 discloses a neoprene adhesive composition, wherein the composition comprises neoprene, a styrene-butadiene-styrene block copolymer, a resorcinol-formaldehyde resin, magnesium oxide, and zinc oxide; relative to 100 parts by weight of chloroprene rubber, the styrene-butadiene-styrene block copolymer is 5-35 parts by weight, the resorcinol-formaldehyde resin is 30-70 parts by weight, the magnesium oxide is 2-8 parts by weight, and the zinc oxide is 2-8 parts by weight. The styrene-butadiene-styrene block copolymer and the resorcinol formaldehyde resin are added into the traditional chloroprene rubber adhesive, so that the prepared adhesive has better adhesive property, and the problem of poor quality of rubber products caused by weak adhesive force of the common chloroprene rubber adhesive to rubber is solved.

However, although the technical scheme overcomes the problem that the single rubber is not firmly bonded in the prior art, the adhesive has strong viscosity but weak durability and is easy to crack in the using process, particularly under the working condition that the temperature exceeds 40 ℃, the bonded part is easy to crack, and the service life of a product using the adhesive is greatly shortened.

In this regard, we conducted intensive studies and filed chinese patent application 201810447085.6, and provided a method for bonding rubber articles, comprising the steps of: (1) grinding and dispersing chloroprene rubber and a styrene-butadiene-styrene block copolymer, adding cyclopentane, stirring until the chloroprene rubber and the styrene-butadiene-styrene block copolymer are fully dissolved, then adding peroxybenzoic acid, controlling the reaction temperature, and obtaining a composition A after the reaction is finished; (2) dissolving raw nitroso-fluoro rubber in dimethoxymethane at the mass concentration of 50-60% to prepare a solution, thus obtaining a composition B; (3) mixing the composition A, the composition B, butyl acrylate, a cross-linking agent, magnesium oxide and zinc oxide to obtain a chloroprene rubber adhesive; (4) coating a layer of silicone grease on the corresponding bonding positions respectively, heating at 40-50 ℃ for 10-15min, and wiping the silicone grease clean by using ethanol; (5) and coating a chloroprene rubber adhesive on the corresponding clean bonding position, and compacting the corresponding bonding position after 3-5 min. Although the adhesive has high viscosity and can improve the adhesion durability, the cyclopentane is used for dissolving chloroprene rubber and styrene-butadiene-styrene block copolymer, the dissolving is difficult, the process is long, and the cyclopentane has severe limitation on the using condition, so the popularization of the adhesive and the adhesion method is determined, and the application disadvantage is large.

Therefore, how to further improve the adhesion method to provide a neoprene adhesive with high viscosity and improved adhesion durability is a problem to be solved in the environment protection.

Disclosure of Invention

The invention aims to provide a bonding method of a rubber product, which applies an adhesive with strong adhesiveness and lasting adhesiveness, overcomes the defects of weak adhesiveness and insufficient durability of the adhesive in the prior art, and has the advantages of simple process, environmental protection and higher popularization and application values.

In order to achieve the above object, the present invention provides a method for preparing a chloroprene rubber adhesive, comprising the steps of:

(1) grinding the chloroprene rubber, adding a hexane hydrocarbon solvent, and stirring until the chloroprene rubber is fully dissolved, wherein the mass concentration of the chloroprene rubber is 50-60%, so as to obtain a composition A;

(2) dissolving raw nitroso-fluoro rubber in dimethoxymethane at the mass concentration of 50-60% to prepare a solution, thus obtaining a composition B;

(3) and mixing the composition A, the composition B, tackifying resin, a crosslinking agent, magnesium oxide and zinc oxide to obtain the chloroprene rubber adhesive.

The invention also provides a chloroprene rubber adhesive prepared by the preparation method.

According to the technical scheme, the chloroprene rubber is ground, the hexane hydrocarbon solvent is added, the mixture is stirred until the chloroprene rubber is fully dissolved, and on the other hand, the composition B containing the nitroso-fluoro rubber raw rubber, the tackifying resin, the cross-linking agent, the magnesium oxide and the zinc oxide are combined to obtain the adhesive with high viscosity and bonding durability. Moreover, the preparation method of the adhesive is simple, environment-friendly, easy to control the bonding process and high in popularization and application value.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In order to achieve the above object, the present invention provides a method for preparing a chloroprene rubber adhesive, comprising the steps of:

(1) grinding the chloroprene rubber, adding a hexane hydrocarbon solvent, and stirring until the chloroprene rubber is fully dissolved, wherein the mass concentration of the chloroprene rubber is 50-60%, so as to obtain a composition A;

(2) dissolving raw nitroso-fluoro rubber in dimethoxymethane at the mass concentration of 50-60% to prepare a solution, thus obtaining a composition B;

(3) and mixing the composition A, the composition B, tackifying resin, a crosslinking agent, magnesium oxide and zinc oxide to obtain the chloroprene rubber adhesive.

According to the technical scheme, the chloroprene rubber is ground, the hexane hydrocarbon solvent is added, the mixture is stirred until the chloroprene rubber is fully dissolved, and on the other hand, the composition B containing the nitroso-fluoro rubber raw rubber, the tackifying resin, the cross-linking agent, the magnesium oxide and the zinc oxide are combined to obtain the adhesive with high viscosity and bonding durability. Moreover, the preparation method of the adhesive is simple, environment-friendly, easy to control the bonding process and high in popularization and application value.

In the above solution, the synthesis of liquid nitroso-fluoro rubber raw rubber is described in patent application 201310133404.3.

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesiveness and high adhesion durability and to improve the adhesion effect, the hexane hydrocarbon solvent is preferably a mixture of n-hexane and cyclohexane in a ratio of 1: 2-3. In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesion and high adhesion durability and to improve the adhesion effect, it is preferable that the amount of the composition B is 40 to 50 parts, the amount of the tackifier resin is 8 to 10 parts, the amount of the crosslinking agent is 10 to 15 parts, the amount of the magnesium oxide is 2 to 3 parts, and the amount of the zinc oxide is 2 to 3 parts, by mass, based on 100 parts of the composition a.

In a more preferred embodiment of the present invention, in order to obtain an adhesive with high adhesion and high adhesion durability and improve the adhesion effect, it is preferable that an anti-aging agent and an antioxidant are further added in step (3).

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesiveness and high adhesion durability and to improve the adhesion effect, it is preferable that,

wherein, the anti-aging agent is used in an amount of 0.5 to 2 parts by weight and the antioxidant is used in an amount of 0.5 to 2.5 parts by weight, based on 100 parts by weight of the composition A.

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesiveness and high adhesion durability and to improve the adhesion effect, the tackifier resin is preferably at least one of rosin, polymerized rosin, rosin glyceride, rosin pentaerythritol ester, petroleum resin, terpene resin, and rosin-modified phenol resin.

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesion and high adhesion durability and to improve the adhesion effect, the chloroprene rubber is preferably a chloroprene rubber having an elongation at break of 850-.

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesion and high adhesion durability and to improve adhesion, it is preferable that the inherent viscosity of the raw nitroso-fluoro rubber is 0.05 to 0.06dLg^-1The physical form of the material is liquid form and has room temperature flowability.

In a more preferred embodiment of the present invention, in order to obtain an adhesive having high adhesion and high adhesion durability and to improve the adhesion effect, the crosslinking agent is preferably one or a combination of two or more of organic polyamine, low molecular weight polyetheramine, aziridine, and polycarbodiimide.

The material of the corresponding bonded substrate may be one or more of a rubber bottom, a cowhells bottom, a multi-layer bottom, a foam bottom and a composite bottom, and may also be polyvinyl chloride plastic, rubber and the like, which can achieve the effects of the present invention, and thus, the description thereof is omitted. In the following embodiments, the base material of the corresponding bonding part is rubber.

The invention also provides a chloroprene rubber adhesive prepared by the preparation method.